Hydrogen-bonded supramolecular architecture in nonlinear optical ammonium 2,4-dinitrophenolate hydrate

Single crystals of ammonium 2,4-dinitrophenolate hydrate (ADH) were grown by the slow evaporation solution growth technique. The structure is elucidated by single-crystal X-ray diffraction analysis and the crystal belongs to an orthorhombic system with noncentrosymmetric space group Pna2₁. The second harmonic generation efficiency of ADH is superior to that of the reference material KH₂PO₄. The X-ray study reveals that molecules are associated by weak C—H...O, O—H...N, N—H...π and π–π stacking interactions, which are responsible for the formation and strengthening of the supramolecular assembly. Inter- and intramolecular hydrogen-bonding interactions support the supramol­ecular architecture in the crystal packing. Three different types of architecture, i.e. column-like packing, a sandwich model of packing and a cluster network type of infrastructure, are observed. Optical studies reveal that the absorption is minimum in the visible region and the cutoff wavelength is at ∼240 nm. The band-gap energy was estimated by the application of the Kubelka–Munk algorithm. The powder X-ray diffraction pattern reveals the good crystallinity of the as-grown specimen. Investigation of the intermolecular interactions and crystal packing using Hirshfeld surface analysis, based on single-crystal X-ray diffraction, reveals that the close contacts are associated with molecular interactions. Fingerprint plots of Hirshfeld surfaces were used to locate and analyze the percentage of hydrogen-bonding interactions.

Computing details

Program(s) used to solve structure: olex2.solve (Bourhis et al., 2013); program(s) used to refine structure: olex2.refine (Bourhis et al., 2013); molecular graphics: Olex2 (Dolomanov et al., 2009); software used to prepare material for publication: Olex2 (Dolomanov et al., 2009).

(I)

Crystal data

C6H3N2O5·H2O·H4N	F(000) = 456.3395
Mr = 219.15	Dx = 1.598 Mg m^−3
Orthorhombic, Pna21	Mo Kα radiation, λ = 0.71073 Å
a = 9.0136 (12) Å	µ = 0.14 mm^−1
b = 21.500 (3) Å	T = 293 K
c = 4.7005 (6) Å	Needle, clear yellowish yellow
V = 910.9 (2) Å^3	0.35 × 0.3 × 0.3 mm
Z = 4

Data collection

Oxford Gemini diffractometer	1402 reflections with I ≥ 2u(I)
Radiation source: Molybdenum, MO	Rint = 0.021
Molybdenum monochromator	θmax = 26.4°, θmin = 3.0°
Detector resolution: 8 pixels mm^-1	h = −10→11
ω rotation scans	k = −8→26
2420 measured reflections	l = −4→5
1681 independent reflections

Refinement

Refinement on F^2	Primary atom site location: iterative
Least-squares matrix: full	All H-atom parameters refined
R[F^2 > 2σ(F^2)] = 0.039	w = 1/[σ^2(Fo^2) + (0.0326P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.083	(Δ/σ)max < 0.001
S = 1.03	Δρmax = 0.19 e Å^−3
1681 reflections	Δρmin = −0.22 e Å^−3
171 parameters	Absolute structure: Flack, H. D. (1983). Acta Cryst. A39, 876-881.
0 restraints	Absolute structure parameter: −2.1 (6)
0 constraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	−0.50318 (18)	−0.41603 (8)	−0.4692 (4)	0.0405 (4)
O6	−0.0408 (2)	−0.52882 (11)	−0.5842 (5)	0.0479 (5)
N1	−0.3503 (3)	−0.53313 (12)	−0.4783 (5)	0.0399 (5)
N2	−0.2809 (2)	−0.38420 (10)	−0.8974 (5)	0.0432 (5)
N3	−0.3802 (3)	−0.16993 (11)	−0.6925 (5)	0.0543 (6)
O2	−0.3142 (2)	−0.43857 (9)	−0.8963 (4)	0.0586 (6)
O4	−0.2946 (3)	−0.15656 (9)	−0.8823 (5)	0.0796 (7)
O3	−0.1798 (2)	−0.36468 (10)	−1.0442 (5)	0.0788 (8)
C1	−0.4709 (2)	−0.36009 (11)	−0.5251 (5)	0.0332 (5)
C2	−0.3640 (3)	−0.34029 (11)	−0.7294 (5)	0.0330 (5)
C4	−0.4096 (3)	−0.23405 (12)	−0.6343 (5)	0.0395 (6)
C3	−0.3349 (3)	−0.27838 (13)	−0.7790 (6)	0.0395 (6)
O5	−0.4414 (4)	−0.13043 (10)	−0.5515 (5)	0.0972 (10)
C5	−0.5129 (3)	−0.24994 (13)	−0.4311 (6)	0.0463 (7)
C6	−0.5413 (3)	−0.31081 (13)	−0.3795 (5)	0.0434 (7)
H5	−0.561 (3)	−0.2185 (12)	−0.327 (6)	0.049 (8)*
H6	−0.610 (3)	−0.3229 (13)	−0.256 (6)	0.050 (8)*
H6a	−0.024 (4)	−0.5152 (16)	−0.742 (9)	0.075 (14)*
H1a	−0.383 (3)	−0.4933 (16)	−0.478 (7)	0.061 (9)*
H3	−0.268 (3)	−0.2679 (12)	−0.928 (7)	0.050 (8)*
H1b	−0.378 (3)	−0.5516 (16)	−0.317 (8)	0.067 (11)*
H6b	−0.006 (4)	−0.5639 (18)	−0.577 (11)	0.119 (17)*
H1c	−0.399 (3)	−0.5585 (15)	−0.627 (7)	0.071 (10)*
H1d	−0.253 (3)	−0.5284 (14)	−0.495 (7)	0.065 (10)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0487 (9)	0.0307 (9)	0.0421 (10)	−0.0033 (8)	0.0086 (7)	0.0044 (8)
O6	0.0518 (11)	0.0410 (12)	0.0508 (14)	0.0054 (10)	0.0003 (9)	0.0023 (11)
N1	0.0447 (14)	0.0294 (12)	0.0457 (15)	−0.0029 (11)	−0.0020 (12)	0.0045 (12)
N2	0.0422 (11)	0.0346 (12)	0.0526 (14)	0.0036 (11)	0.0110 (10)	0.0076 (12)
N3	0.0723 (16)	0.0307 (14)	0.0600 (17)	−0.0010 (13)	0.0034 (13)	0.0028 (13)
O2	0.0742 (13)	0.0302 (10)	0.0713 (13)	0.0004 (10)	0.0275 (12)	−0.0025 (10)
O4	0.0962 (16)	0.0360 (12)	0.1067 (17)	−0.0056 (12)	0.0379 (16)	0.0150 (13)
O3	0.0759 (14)	0.0426 (12)	0.118 (2)	0.0088 (11)	0.0624 (14)	0.0157 (13)
C1	0.0346 (12)	0.0294 (13)	0.0358 (14)	−0.0021 (11)	−0.0033 (10)	0.0019 (11)
C2	0.0342 (12)	0.0287 (13)	0.0362 (13)	0.0027 (11)	0.0032 (10)	0.0022 (11)
C4	0.0472 (14)	0.0273 (13)	0.0440 (16)	−0.0012 (11)	−0.0009 (12)	0.0025 (12)
C3	0.0395 (14)	0.0336 (14)	0.0455 (16)	0.0004 (12)	0.0048 (12)	0.0058 (12)
O5	0.168 (3)	0.0326 (12)	0.0914 (19)	0.0035 (15)	0.0511 (19)	−0.0091 (14)
C5	0.0627 (17)	0.0334 (14)	0.0428 (16)	0.0061 (14)	0.0068 (14)	−0.0068 (13)
C6	0.0489 (15)	0.0390 (15)	0.0424 (16)	−0.0013 (13)	0.0136 (13)	−0.0017 (13)

Geometric parameters (Å, º)

O1—C1	1.265 (3)	N3—C4	1.430 (3)
O6—H6a	0.81 (4)	N3—O5	1.210 (3)
O6—H6b	0.82 (4)	C1—C2	1.425 (3)
N1—H1a	0.91 (3)	C1—C6	1.412 (3)
N1—H1b	0.89 (4)	C2—C3	1.376 (3)
N1—H1c	0.99 (4)	C4—C3	1.351 (3)
N1—H1d	0.89 (3)	C4—C5	1.377 (3)
N2—O2	1.207 (3)	C3—H3	0.95 (3)
N2—O3	1.218 (3)	C5—C6	1.355 (4)
N2—C2	1.441 (3)	C5—H5	0.94 (3)
N3—O4	1.213 (3)	C6—H6	0.89 (3)
H6b—O6—H6a	108 (4)	C1—C2—N2	121.7 (2)
H1b—N1—H1a	109 (3)	C3—C2—N2	116.2 (2)
H1c—N1—H1a	112 (3)	C3—C2—C1	122.1 (2)
H1c—N1—H1b	103 (3)	C3—C4—N3	119.4 (2)
H1d—N1—H1a	102 (3)	C5—C4—N3	119.8 (2)
H1d—N1—H1b	114 (3)	C5—C4—C3	120.8 (2)
H1d—N1—H1c	116 (3)	C4—C3—C2	120.1 (2)
O3—N2—O2	121.5 (2)	H3—C3—C2	118.3 (17)
C2—N2—O2	120.2 (2)	H3—C3—C4	121.3 (16)
C2—N2—O3	118.3 (2)	C6—C5—C4	119.4 (3)
C4—N3—O4	119.1 (2)	H5—C5—C4	119.7 (16)
O5—N3—O4	121.7 (2)	H5—C5—C6	120.9 (16)
O5—N3—C4	119.1 (2)	C5—C6—C1	123.6 (3)
C2—C1—O1	125.4 (2)	H6—C6—C1	114.3 (18)
C6—C1—O1	120.6 (2)	H6—C6—C5	122.0 (18)
C6—C1—C2	114.0 (2)